Quinoyl alkanesulfonates and toluenesulfonates

ABSTRACT

Novel compounds of the classes of halopyridyl or haloquinolyl alkanesulfonates, including haloalkanesulfonates, and halopyridyl or haloquinolyl Alpha -toluenesulfonates, are useful as agricultural toxicant compositions. The compounds are prepared by the reaction, in the presence of a hydrogen halide acceptor, of an appropriate halogenated pyridinol or quinolinol with an appropriate alkanesulfonyl halide or an appropriate Alpha toluenesulfonyl halide. The compounds are also prepared by the reaction of an alkali metal salt of the halogenated pyridinol or quinolinol with the alkanesulfonyl halide or the Alpha toluenesulfonyl halide.

United States Patent 1 Hamer 51 Feb. 27, 1973 QUINOYL ALKANESULFONATESAND TOLUENESULFONATES [75] Inventor: MartinHamer,Skokie,lll.

[73] Assignee: International Minerals & Chemical Corporation [63]Continuation-in-part of Ser. No. 645,898, June 14,

1967, Pat. No. 3,535,324.

[52] US. Cl. ..260/283 S, 71/94, 260/289, 260/283 CN, 424/258 [51] Int.Cl. ..C07d 33/60 [58] Field of Search..... ..260/283 8, 289 0X [56]References Cited UNITED STATES PATENTS 3,284,459 11/1966 Wilbert..260/287 R 3,297,525 1/1967 Grier ....260/287 R 3,298,911 l/1967 Renz....260/287 R 2,178,571 11/1939 Flett ........260/289 3,228,827 1/ 1966Larson ..260/456 P OTHER PUBLICATIONS Burger, Medicinial Chemistry,Interscience 1960, p 1123, 1130.

Buchmann, abstracted in Chem ABSTR Vol 53 C01 2229-2230 (1959).

Primary ExaminerDonald G. Daus Attorney-James E. Wolber and PeterAndress [57] ABSTRACT Novel compounds of the classes of halopyridyl orhaloquinolyl alkanesulfonates, including haloalkanesulfonates, andhalopyridyl or haloquinolylatoluenesulfonates, are useful asagricultural toxicant compositions. The compounds are prepared by thereaction, in the presence of a hydrogen halide acceptor, of anappropriate halogenated pyridino] or quinolinol with an appropriatealkanesulfonyl halide or an appropriate a-toluenesulfonyl halide. Thecompounds are also prepared by the reaction of an alkali metal salt ofthe halogenated pyridinol or quinolinol with the alkanesulfonyl halideor the a-tolucnesulfonyl halide.

9 Claims, No Drawings QUINOYL ALKANESULFONATES AND 'IOLUENESULFONATESCROSS REFERENCE TO RELATED APPLICATION This application is acontinuation-in-part of'application Ser. No. 645,898, filed June 14,1967, now U.S. Pat. No. 3,535,324.

BACKGROUND OF THE INVENTION This invention relates to a new class ofcompounds which are useful as pesticides, e.g., insecticides andnematocides, and the preparation of the same. More particularly, thisinvention relates to compounds which are especially useful forcontrolling soil-dwelling nematodes.

Many species of soil-dwelling nematodes are plant parasites which attackand cause damage to crops and ornamental plants. They are particularlydestructive to plants in areas of sandy soil and mild climaticconditions. Nematodes may do some direct damage to the stems and leavesof plants, but they do most damage below the soil surface. Nematodesdamage plant roots by killing the living cells or interfering with thenormal functioning of living cells, that is, by causing the plant toreact with the formation of galls or knots on the roots.

Many methods have been used in the past for controlling plant parasiticnematodes. One of the most useful measures for controlling nematodeinfestation is chemical treatment. The most effective commercialnematocides, at the present, are volatile compounds which are injectedinto soil. These compounds volatilize and diffuse in all directions togive a relatively high degree of control in the surface few feet of thesoil. These nematocides, although highly effective, suffer from thedisadvantages that they are short-lived in the soil and somewhatdifficult to apply. Consequently, considerable effort has been recentlyexpended in the development of a nematocide which is more easily appliedand more residual in the soil. U.S. Pat. No. 3,228,827, issued Jan. 11,1966, discloses that the 2,4- dihalophenyl esters of loweralkanesulfonic acids and of lower haloalkanesulfonic acids are effectivenonvolatile nematocides with long residual activity. The compound2,4-dichlorophenyl methanesulfonate has been reported to be outstandingboth in degree of activity and in long residual effect.

SUMMARY OF THE INVENTION This invention is based on the discovery of newnonvolatile nematocides with long residual activity, which compounds arealso effective insecticides. In accordance with the present invention,growing plants are protected from plant-attacking nematodes and insectsby treating the environment thereof (i.e., the locus where control is tobe effected) with a non-phytotoxic pesticidally-effective quantity of ahalopyridyl alkanesulfonate, including a halopyridylhaloalkanesulfonate, or a halopyridyl a-toluenesulfonate, including ahalopyridyl substituted a-toluenesulfonate, represented by the formula:

H osounn or a haloquinolyl alkanesulfonate, including a haloquinolylhaloalkanesulfonate, or a haloquinolyl atoluenesulfonate, including ahaloquinolyl substituted a-toluenesulfonate, represented by the formula:

The novel compounds of this invention may be prepared by the reaction,in the presence of an acid acceptor (i.e., hydrogen halide acceptor), ofthe appropriate halogenated pyridinol represented by the formula:

or appropriate halogenated quinolinol represented by the formula:

with the appropriate C -C alkanesulfonyl halide, C -C haloalkanesulfonylhalide, a-toluenesulfonyl halide or substituted toluenesulfonyl halide.Alternatively, the compounds of this invention are also convenientlyprepared by thereaction of an alkali metal salt, e.g., sodium orpotassium salt, of one of the aforementioned halogenated pyridinols ofquinolinols with an appropriate one of the aforementioned sulfonylhalides;

In the foregoing formulas, X represents halogen, R is a straight orbranched chain lower alkyl or haloalkyl radical, e.g., alkyl orhaloalkyl radical containing from one to 10 carbon atoms, benzyl or asubstituted benzyl radical, R is methyl or ethyl, m is an integer from 1to 3 inclusive, n is l or 2, and 0 is an integer from 0 to 2, inclusive.It will be evident m, n and 0 will not total more than 5 in theforegoing single-ring compounds. Furthermore, the single-ring compoundswill contain at least one --OSO R (or OI'I) group in the two or threeposition in the ring. The condensed ring compounds of the foregoingformulas may contain the radicals X, OSO R (or -OH), and R all on thebenzene portion thereof (in which event m, n and 0 will not total morethan 4), all on the pyridine portion thereof (in which event in, n and 0will not total more than 3) or on both rings. Preferred compounds arethose wherein X is either chlorine or bromine, R is an alkyl radical orhaloalkyl radical containing from one to four carbon atoms, benzyl, or asubstituted benzyl radical, and m and n total 2 to 4.

The preferred class of compounds of the present invention are the2-pyridyl alkanesulfonates, with 3,5- dichloro-Z-pyridylmethanesulfonate being the preferred compound. Other compounds of thisinvention falling within the foregoing formulas are 3,5-dibromo-Z-pyridyl methanesulfonate, 5-chloro-2- pyridyll-decanesulfonate, 5 chloro-Z-pyridyl methanesulfonate,2,5-dichloro-3-pyridyl Z-ethylhexanesulfonate, 6-chloro-2-pyridyla-toluenesulfonate, 2- chloro-3-pyridyl methanesulfonate,2-bromo-3-pyridyl 2-propanesulfonate, 2-bromo-3-pyridylmethanesulfonate, 6-chloro-2-pyridyl l-butanesulfonate, S-chloro-Z-pyridyl 2,3-dichloro-l-propanesulfonate, 6-chloro-2- pyridyl2-bromo-l-ethanesulfonate, 3,5,6-trichloro-2- pyridyl methansulfonate,6-chloro-3,5-dibromo-2- pyridyl methanesulfonate,3,5-dichloro-6-methyl-2- pyridyl methanesulfonate, -bromo-8-quinolylmeth ane-sulfonate, 7-chloro-4-quinolyl lchloroethanesulfonate,4-chloro-8-quinolyl ethanesulfonate, 5-chloro-8-quinolymethanesulfonate, 5,7- dibromo-8-quinolyl methanesulfonate,5,7-dichloro-8- quinolyl methanesulfonate, 8-chloro-4-quinolylethanesulfonate, 8-chloro-4-quinolyl l-hexanesulfonate,6-chloro-2-quinolyl l-pentanesulfonate, 3,6- dichloro-2-quinolyl2-propanesulfonate, 8-chloro-6- quinolyl methanesulfonate,7-bromo-3-quinolyl l-octanesulfonate, 2,4-dichloro-7-quinolyl 2-ethylhexanesulfonate, 2-chloro-5-quinolyl l-propanesulfonate,4-chloro-7-quinolyl ethanesulfonate, 5-chlor0-8-quinolyll-decanesulfonate, and 5,7-dibromo-8-quinolyl 3- chloropropanesulfonate.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In one aspect, therefore, thepresent invention relates to the preparation of novel compounds usefulas agricultural toxicant compositions, viz., nematocides andinsecticides, by the reaction of a halogenated pyridinol or quinolinolwith a sulfonyl halide in the presence of a hydrogen halide acceptor.

Useful halogenated pyridinols or quinolinols include3,5-dichloro-2-pyridinol, 5-bromo-8-quinolinol, 5- chloro-2-pyridinol,5-chloro-8-quinolinol, 6-chloro-2- pyridinol, 3-chloro-2-pyridinol,3-bromo-2-pyridinol, 5,7-dibromo-8-quinolinol,5,7-dichloro-8-quinolinol, 5-iodo-2-pyridinol, 5,7-diiodo-8-quinolinol,6-bromo- Z-pyridinol, 3,5,6-trichloro-2-pyridinol, 6-chloro-3,5-dibromo-Z-pyridinol, 5-bromo-2-pyridinol, 3,5- dibromo-Z-pyridinol,5-chloro-6-methyl-2-pyridinol, 5-bromo-6-methyl-2-pyridinol,3,5-dichloro-6-methyl- 2-pyridinol, 8-chloro-4-quinolinol,6-chloro-2-quinolinol, 3,6-dichloro-2-quinolinol, 8-chloro-6-quinolinol,7-bromo-3-quinolinol, 2,4-dichloro-7-quinolinol, 2-chlor0-5-quinolinol,4-chloro-7-quinolinol, and 3,5-dibromo-6-methyI-Zpyridinol.

Sulfonyl halides which are useful in the present invention includealkaneand haloalkanesulfonyl halides such as methanesulfonyl chloride,l-butanesulfonyl chloride, l-propanesulfonyl chloride, 2-propanesulfonylchloride, hpentanesulfonyl chloride, l-octane sulfonyl chloride,l-decanesulfonyl chloride, lchlorethanesulfonyl chloride, 2-chloro-l-ethanesulf0- nyl chloride, 2,3-dichloro-l-propanesulfonyl chloride,l,2-dichloroethanesulfonyl chloride, ethanesulfonyl chloride,trichloromethanesulfonyl chloride, chloromethanesulfonyl chloride,Z-ethylhexanesulfonyl chloride, and bromomethanesulfonyl chloride.Other' useful sulfonyl halides include 'a-toluenesulfonyl halides suchas a-toluenesulfonyl chloride and atoluenesulfonyl bromide andsubstituted a-toluenesulfonyl halides, i.e., compounds containingsubstituents on the phenyl ring which are inert under the reactionconditions such as halo (e.g. chloro,bromo, and iodo), cyano, nitro andmethyl. Examples of such substituted a-toluenesulfonyl halides include4-chloro-atoluenesulfonyl chloride, 4-bromo-a-toluenesulfonyl chloride,2,4-dichloro-a-toluenesulfonyl chloride, 4- nitro-a-toluenesulfonylchloride, 4-cyano-atoluenesulfonyl chloride, 4-methyl-a-toluenesulfonylchloride.

The relative proportions of the reactants in preparing the novelcompounds of this invention may vary over a relatively wide rangeGeneralIy an excess of either the halogenated nyridinol (or quinolinol)or the sulfonyl halide and hydrogen halide acceptor may be used. Thesulfonyl halide is preferably employed in at least a stoichiometricamount and more preferably in a slight excess. A slight excess of thehydrogen halide acceptor is also preferably utilized except when it alsoserves as the reaction medium, as hereinafter described, and greaterquantities are required. For example, in the preparation of compounds ofthis invention containing only one sulfonate group, that is, when n inthe foregoing formulas is one, the mole ratios of the sulfonyl halideand hydrogen halide acceptor (which is not the reaction medium) to thehalogenated pyridinol (or quinolinol) will be in the range of from about0.511 to about 4: l preferably from about 1:1 to about 2: l.

The reaction is carried out in a non-aqueous reaction medium, i.e., asolvent or mixture of solvents, which does not interfere with thedesired reaction. Suitable reaction media include inert solvents such asketones, e.g., butanone and acetone, halogenated hydrocarbons, e.g.,ethylene dichloride and chlorobenzene, aromatic hydrocarbons, e.g.,benzene and toluene, esters, e.g., ethyl acetate, and ethers, e.g.,dioxane. In some instances the same material, pyridine as for example,may serve the dual function of a solvent and an acid acceptor. Thereactants may be dissolved together in the same solvent, or individuallyin separate quantities of the same or different solvents comprising thereaction medium, which quantities of solvents are then combined.

Bases in addition to pyridine which are useful as hydrogen halideacceptors in the reaction of the instant invention include sodium orpotassium hydroxide, sodium or potassium carbonate, and tertiary aminessuch as triethylamine, tripropylamine, dimethyl aniline, and substitutedpyridines such as the lutidines and picolines.

Reaction temperatures in the range of about room temperature, e.g., 20C., up to about the reflux temperature of the reaction mixtures, andeven higher, are useful. The reaction is preferably carried out at anelevated temperature of from about 40 to about C. to obtain' maximumyield for a given length of reaction time when the non-aqueous system isemployed. In general, reaction temperatures in the preferred range willprovide an increase in yield and a reduction in the time required forcompletion of the reaction as compared to reaction temperatures outsideof the preferred range. Satisfactory yields are obtained when thereaction mixture is maintained in the preferred range for at least aboutl5 minutes. However, maximum yields are obtained when longer reactiontimes, e.g., up to about six hours or longer, are used.

The product is separated from the by-product hydrogen halide salt of theacceptor and recovered by conventional techniques, as for example, byextraction, distillation, filtration, crystallization and combinationsof these techniques.

In another aspect, this invention relates to the preparation of thecompounds of this invention by the reaction, in a suitable inertreaction medium, of an alkali metal salt, e.g., sodium or pota siumsalt, of a halogenated pyridinol or quinolinol of the foregoing formulaswith a sulfonyl halide as hereinbefore described.

The relative proportions of the reactants in this method may also varyover a relatively wide range and an excess of either of the reactantsmay be used. However, it is preferred to employ the sulfonyl halide inat least a stoichiometric amount.

The reaction mixtures for carrying out this method may be prepared in avariety of ways. For example, the sulfonyl halide (neat or in solutionin a solvent such as benzene), is added to a solution or dispersion ofthe salt of the halogenated pyridinol or quinolinol. Alternatively, thesalt of the may halogenated pyridinol or quinolinol may be added to asolution of the sulfonyl halide, or the two reactants may besimultaneously added to a suitable reaction medium. The aforementionedreaction media are generally useful for this method of preparation also.

The compounds are most conveniently prepared by the addition of thesulfonyl halide (neat or in solution in a water-immiscible organicsolvent) to an aqueous solution of the salt of the halogenated pyridinolor q'uinolinol. This method facilitates the separation of the by-producthydrogen halide salt from the product sulfonate. The by-product remainsin solution in the aqueous phase and the product sulfonate eitherprecipitates when the sulfonyl halide is added neat or remains insolution when the sulfonyl halide is added in solution in a solvent inwhich the product sulfonate is also soluble. The product sulfonate isrecovered from the organic solvent by conventional techniques such as byevaporation of the solvent. Furthermore, the reaction is essentiallycomplete in about fifteen minutes at room temperature and affords a goodyield of a product of good quality. Maximum yields are obtained when apH of about 9 to 12 is maintained during the reaction by the addition ofa suitable base.

The compounds of this invention are utilized in still another aspect tocontrol nematodes and insects by applying a toxic amount of the same tothe loci of infestation or potential infestation. The compounds may beadvantageously employed forprotecting growing plants from soil-dwellingnematodes by disseminating a nematocidally effective quantity of thecompounds in the soil. Soil-dwelling nematodes which may be controlledby the compounds of this invention include cyst-forming nematodes of thegenus Heterodera, endoparsitic nematodes, e.g., of the generaDitylenchus, Meloidogyne, Nacobbus, Pratylenchus, etc., andectoparasitic nematodes, e.g., of the genera Belanolaimus, Cacopaurus,Dolichodorus, Trichodorus, etc.

The amount of the compounds of this invention which are introduced intothe soil for achieving effective control of soil-dwelling nematodes willvary within wide limits depending upon factors, among others, as thetime of application, climatic conditions, the method of application, thenumber of applications, the activity of the specific compound beingutilized, and the like. Effective concentrations of the compounds forthe control of soil-dwelling nematodes will generally lie within therange of from about 2 to about 200 pounds per acre of land. Generallyapplication rates of from about 5 to about 100 pounds of the compoundsper acre are preferred.

Most compounds of this invention are solids at ordinary temperaturesand, accordingly, may be applied to the soil in a variety of forms. Forexample, they may be applied to the soil by merely being mixed, infinely divided form, with the soil to be treated. Alternatively, theymay be applied to the soil in admixture with a suitable inert solidcarrier. For example, the compounds may be mechanically mixed or groundwith an inert solid diluent such as talc, mica, a clay such as one ofthe bentonites, fullers earth and the like. Alternatively, the compoundsmay be dissolved in a suitable solvent which is then mixed with thesolid diluent and evaporated during or after the mixing operation.

The sulfonates may also be applied to the soil while in a solution,dispersion, or emulsion, in a suitable inert liquid medium such aswater. Water is preferred for the purpose of convenience and economy.Inasmuch as the sulfonates of this invention are not very soluble inwater, water-base spray solutions of the compounds can be prepared bydissolving at least one of the compounds in a suitable organic liquidsuch as acetone to form a concentrated solution which is then mixed witha much larger volume of water to form a dispersion or solution of thedesired concentration. Alternatively, the compounds of this inventioncan be emulsified in water by the employment of a suitable emulsifyingagent, and the emulsion is then applied to the soil. Representativeemulsifying agents include alkali metal salts of long chain aliphaticsulfates and alkylaryl sulfonates, wholly or partially neutralizedsulfuric acid derivatives or petroleum oil, polyoxyalkylene derivativesof phenols and fatty acids, and the like.

Alternatively, the compounds may also be applied to the soil insolutions in suitable water-immiscible organic solvent such as benzene,kerosene, chlorinated hydrocarbons, xylene, and various non-phytotoxichydrocarbon fractions which are ordinarily used for such purposes, e.g.,spray oils.

Another method of utilizing the compounds of this invention forprotecting plants from soil-dwelling nematodes is to dip the roots ofplants being transplanted in a solution, dispersion or emulsioncontaining a nematocidally effective quantity, e.g., about 20 to about10,000 ppm, of a sulfonate of this invention. This method is especiallyuseful for protecting plants such as tomato and tobacco which arenormally transplanted during some stage of growth.

The compounds of this invention may also be used for combatingabove-ground feeder nematodes of the genera Anguina, Aphelenchoides andDitylenchus and insects, e.g., aphids. For these uses, the sulfonatesuseful in accordance with the present invention may be similarlyemployed in the form of solutions, dispersions or emulsions, wettablepowders and dusts. A solution, dispersion or emulsion of one of thecompound is generally pesticidally effective when it contains about 20to about 10,000 parts per million of the sulfonate. The solution,dispersion or emulsion is usually sprayed on the plants in a sufficientquantity so that the material just begins to run off the leaves andstems. It is also possible to apply a paste containing a compound ofthis invention to the stern, branch or trunk of a tree or bush.

The following non-limiting examples will serve to further illustratethis invention.

Mcthanesulfonyl chloride, 11.5 grams (0.10 mole), was added dropwise inabout 2 minutes to a solution of 18.0 grams (0.10 mole) of-chloro-8-quinolinol in 150 milliliters of pyridine. The resultingsolution was heated at reflux for 2 hours, and then allowed to standovernight and cool slowly. A number of crops of pyridine hydrochloridecrystallized. The final filtrate was evaporated to dryness and the crudeproduct purified by recrystallization from heptane. A total of 5.3 grams(27 percent yield) of pure 5-chloro-8-quinolyl methanesulfonate, mp.106-l07 C. was obtained. Analysis: Calculated for c,,,H,c|No,s: 13.65%Cl; 5.38% N; 12.10% S. Found: 13.76% Cl; 5.44% N; 12.44% S.

EXAMPLE ll Methanesulfonyl chloride in the amount of l 1.5 grams (0.10mole) was added to a solution of 30.3 grams (0.10 mole) of5,7-dibromo-8-quinolinol and 7.9 grams (0.10 mole) of dried pyridine in250 milliliters of benzene. The resulting mixture was heated at refluxfor 4 hours and then allowed to cool. The cooled reaction mixture wasstirred with 250 milliliters of water and filtered. The solid removed bythe filtration was 15.1 grams of unreacted 5,7-dibromo-8-quinolinol. Thebenzene layer was separated, washed with water until neutral, andevaporated to leave a solid. The solid was purified by recrystallizationfrom chloroform and then 2-butanone to give 7.2 grams 19 percent yield)of pale tan crystals of 5,7-dibromo-8-quinolyl methanesulfonate. Theproduct melted at l72.5-l 73.5 C. Analysis: Calculated for C l'l Br- NOS: 3.68% N; 8.40% S. Found: 3.82% N; 8.03% S.

EXAMPLE Ill The nematocidal activity of 3,5-dichloro-2-pyridylmethanesulfonate was compared in the following tests with thenematocidal activity of 2,4-dichlorophenyl methanesulfonate of U. 8.Pat. No. 3,228.827 and several commercially available nematocides.

In these tests, the procedure consisted of thoroughly mixing the testcompound with a quantity of soil heavily infested with the root-knotnematode (Meloidogyne sp.) in an amount to provide the desired dosage ofthe test compound in the soil. The soil was rolled, held for 48 hours incapped jars, and then transferred to clay seedling A seeding tomato(Rutgers variety) was transplanted into each pot. After about 4 or 5weeks each tomato plant was removed from the soil, the soil was washedfrom the roots of the plant, and the amount of galling caused by thenematodes was compared by experienced observers with tomato seedlingsplanted in untreated nematode-infested soil.

The dosage use and the amount of galling obtained at each dosage of thetest compounds is set out in Table 1. Each number indicated at eachdosage level stands for the control obtained in a separate test. Thefollowing rating scale was used:

5 is no galling or 100 percent control.

4 is very light galling.

3 is light galling.

2 is moderate galling.

l is severe galling, equal to plants in untreated soil.

TA BLE l Dosage, Compound lbs/acre Control 3,5-Dichloro-2-pyridyl 37 5,5 ,5 methanesulfonate 18 5 ,5 ,5 9 4,4,4 4.5 4,4,3 2,4-Dichlorophenyl37 4,4 ,4 methanesulfonate l8 3 ,2 ,2 9 2,2,2 4.5 l ,l ll-chloro-2,3-dibromopropane 37 4,4 18 3 ,3 9 l l PhenylN,N'-dimethylphosphoro- 37 4,5,4,4 diamidate l8 3,3,4,4 9 2,2,3 ,33,5-Dimethyl-2,3,5,2H-tetra- 37 5 ,5 hydrothiadiazine-Z-thionc 18 5,5 I9 3 ,3

The above data clearly demonstrate the superiority in nematocidalactivity of 3,5-dichloro-2-pyridyl methanesulfonate over2,4-dichlorophenyl methanesulfonate. It will be noted that control wasobtained with the former compound at a dosage rate of 37 pounds per acrewhereas there was still some very light galling at the same dosage whenthe latter compound was used. However, when 3,5-dichloro-2- pyridylmethanesulfonate was used at a rate of 4.5 pounds per acre there wasonly very light galling in two of the tests and light galling in thethird test. ln contradistinction, no control was obtained when 2,4-dichlorophenyl methanesulfonate was used at the rate of 4.5 pounds peracre. Similar results will be noted when the activity of3,5-dichloro-2-pyridyl methanesulfonate is compared with the activity ofthe other three compounds, which are commercially available asnematocides.

EXAMPLE lV As illustrative of the nematocidal activity of othercompounds falling within the scope of this invention, 6-chloro-2-pyridyl methanesulfonate and 5-chloro-2- pyridylmethanesulfonate as representative monohalopyridyl alkanesulfonates,6-chloro-2-pyridyl a-toluenesulfonate, as a representative halopyridylatoluenesulfonate, and 5,7-dichloro-8-quinolyl methanesulfonate, as arepresentative haloquinolinyl alkanesulfonate, were tested as above, Theresults of these tests are set out in Table 11.

TABLE II Dosage Compound lbs./acre Control 6-Chloro-2-pyridyl 75 5,4methanesulfonate 37 S-Chloro-Z- yridyl 75 5,5 methancsul onatc 35 4,46-Chloro-2-pyridyl 3,2 a-tolucnesulfonatc 5,7-Dichloro-8-quinolyl 1505,5 methanesulfonate 75 3,2

EXAM PLE V Tests were conducted to compare the insecticidal activity of3,5-dichloro-2-pyridyl methanesulfonate with S-(l,2-dicarbeth-oxyethyl)-0,0-dimethyl phosphorodithioate, a commonly usedcommercial insecticide. ln these tests, a potted Nasturtium plantinfested with the bean aphid (Aphis fabae) was sprayed,

at the desired dosage, to run-off with one of the chemicals under test.After 24 hours the aphids were observed and the degree of control rated.The results of these tests are given in Table Ill.

TABLE lll Kill pf A hids at Compound 50 2 12.5 P PP P3,5-Dichloro-2-pyridyl I80 78 p 20 methanesulfonate S-( l,Ldicarbethoxyethyl)-0,0 I I00 35 dimethyl phosphorodithioatcsubstituent of the wherein X is chlorine, bromine or iodine; R is C Calkyl or C C haloalkyl having from 1 to 3 halogen substituents, benzylor substituted benzyl having on the ring a substituents, benzyl groupconsisting of chlorine, bromine, iodine, nitro, cyano and methyl; R ismethyl or ethyl; m is l or 2; and o is an integer from 0 to 2.

2. A compound in accordance with claim 1 wherein X is chlorine orbromine; and R is C -C alkyl or C,C haloalkyl having from 1 to 3 halogensubstituents, benzyl or substituted benzyl having on the ring asubstituent of the group consisting of chlorine, bromine, iodine, nitro,cyano and methyl.

3. A compound in accordance with claim 2 wherein 0 is 0.

4. A compound in accordance with claim 2 wherein R is alkyl having fromone to four carbon atoms.

5. A compound in accordance with claim 4 wherein said compound has saidOSO R group in the eight position on the condensed ring.

6. A compound in accordance with claim 5 wherein o is 0.

7. A compound in accordance with claim 6 wherein said compound is5,7dichloro-8-quinolyl methanesulfonate.

8. A compound in accordance with claim 6 wherein said compound is5-chloro8-quinolyl methanesulfonate.

9. A compound in accordance with claim 6 wherein said compound is5,7-dibromo-8-quinolyl methanesulfonate.

2. A compound in accordance with claim 1 wherein X is chlorine orbromine; and R is C1-C4 alkyl or C1-C4 haloalkyl having from 1 to 3halogen substituents, benzyl or substituted benzyl having on the ring asubstituent of the group consisting of chlorine, bromine, iodine, nitro,cyano and methyl.
 3. A compound in accordance with claim 2 wherein o is0.
 4. A compound in accordance with claim 2 wherein R is alkyl havingfrom one to four carbon atoms.
 5. A compound in accordance with claim 4wherein said compound has said -OSO2R group in the eight position on thecondensed ring.
 6. A compound in accordance with claim 5 wherein o is 0.7. A compound in accordance with claim 6 wherein said compound is5,7-dichloro-8-quinolyl methanesulfonate.
 8. A compound in accordancewith claim 6 wherein said compound is 5-chloro-8-quinolylmethanesulfonate.
 9. A compound in accordance with claim 6 wherein saidcompound is 5,7-dibromo-8-quinolyl methanesulfonate.